Thiazolylpyrazolinones and their use for protecting technical materials

ABSTRACT

The present invention relates to novel thiazolylpyrazolinones, a process for their preparation and their use for the protection of technical materials.

This application is a 371 of PCT/EP96/01032 filed Mar. 20, 1995.

The present invention relates to novel thiazolylpyrazolinones, a processfor their preparation and their use for the protection of technicalmaterials.

Thiazolylpyrazolinones are known and are described, e.g., in JP-2 149617, Indian. J. Chem. 21 B, 869 (1982), Synth. Com. 23, 1855 (1993), J.heterocyclic Chem. 27, 865 (1990) and DD-150 203. However, their use forthe protection of industrial materials has not been disclosed.

The application relates to novel thiazolylpyrazolinone derivatives ofthe formula ##STR1## in which

R¹, R², R³ independently of each other each represent hydrogen, alkyl orhalogen, and

R⁴ represents hydrogen or unsubstituted or substituted alkyl, alkenyl,alkinyl, cycloalkyl, cycloalkenyl, alkyl (cycloalkyl), alkenyl(cycloalkenyl), alkoxy, alkylthio, aralkoxy, aralkylthio, aralkyl, aryl,hetaryl, aryloxy, hetaryloxy, arylthio, hetarylthio, alkoxycarbonyl,alkoxycarbonalalkyl or cyanoalkyl, or their acid addition products ormetal salt complexes.

In the present application:

Alkyl preferably denotes straight-chain or branched, unsubstituted orsubstituted alkyl having 1 to 18 C atoms, such as Me, Et, n-, i-propyl,n-, i-, s- and tert-butyl, n-, i- and tert-pentyl, n-hexyl, n-octyl,n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetrad ecyl,n-pentadecyl, n-hexadecyl, n-heptodecyl or n-octadecyl or their branchedstructural isomers.

Suitable substituents are preferably halogen, such as chlorine and/orfluorine.

An alkyl radical can also be interrupted by 1 to 2 heteroatoms such asoxygen or sulphur, or atom groups such as N-Me, N-Et, --S(O), --SO₂,without the total number of atoms changing.

Alkenyl (+alkinyl) is preferably defined as alkyl, changed only to theextent that at least one and at most three C--C single bonds have beenreplaced by a C--C double (triple) bond. The number of C atoms is atleast three and is increased by at least two C atoms with each furtherdouble bond (triple bond) which is added.

Cycloalkyl and cycloalkenyl groups include cycloalkyl having preferably3 (5) to 7 C atoms, such as cyclopropyl, cyclobutyl, cycloheptyl,cyclopentyl, cyclopentenyl, cyclohexenyl, cyclohexyl; preferredsubstituted cycloalkyl groups include cycloalkyl substituted by 1 to 3C₁ -C₄ -alkyl groups or 1 to 3 halogen atoms, such as chlorine and/orfluorine, such as methylcyclohexyl, dimethylcyclohexyl,1,3,3-trimethylcyclohexyl, 3-chlorocyclohexyl. Alkyl(cycloalkyl) (andalkyl(cycloalkenyl) groups) preferably contain 1 to 6 C atoms in thestraight-chain or branched alkyl moiety and 3 (5) to 7 atoms in thecycloalkyl/alkenyl moiety; particularly (1-cyclopentyl)methyl,(1-cyclopentenyl)methyl, (1-cyclohexenyl)methyl, (1-cyclohexyl)methyl,(1-cyclopropyl)methyl.

Alkoxycarbonyl represents straight-chain or branched alkoxycarbonylpreferably having 1 to 6 C atoms in the alkoxy radical, such asmethoxycarbonyl, ethoxycarbonyl, n- and i-propoxycarbonyl, n-, i-, sec-and tert-butoxycarbonyl, hexoxycarbonyl. Analogous meanings apply to thealkoxycarbonylalkyl groups.

Aralkyl preferably contains 1 to 6, in particular 1 to 4, C atoms in thestraight-chain or branched alkyl moiety and preferably contains phenylor naphthyl as aryl moiety.

Examples of aralkyl groups of this type include benzyl, α-methyl benzyl,α,α-dimethylbenzyl, 2-phenethyl, α- and β-naphthylmethyl. These aralkylradicals can bear 1 to 3 substituents selected from the group consistingof halogen (in particular chlorine and/or fluorine), nitro, cyano,nonhalogenated or halogenated C₁ -C₄ -alkyl or -alkoxy, such as methyl,ethyl, trifluoromethyl, difluorochloromethyl, difluoromethyl,trichloromethyl, methoxy, ethoxy, trifluoromethoxy,difluorochloromethoxy and difluoromethoxy, non-halogenated orhalogenated C₁ -C₄ -alkylmercapto, such as methylmercapto,trifluoromethylmercapto, difluorochloromethylmercapto.

The term aryl is to be taken to mean unsubstituted or substituted arylpreferably having 6 to 12 C atoms in the aryl moiety. Preferred examplesinclude phenyl, biphenyl and naphthyl. The aryl groups can bear 1 to 3substituents selected from the group consisting of halogen (inparticular chlorine and/or fluorine), C₁ -C₆ -alkyl, -alkoxy orthioalkoxy, halogen-C₁ -C₂ -alkyl (such as trifluoromethyl,difluoromethyl), cyano, nitro, C₁ -C₆ -alkoxycarbonyl or amino.

The term alkoxy is to be taken to mean straight-chain and branchedalkoxy preferably having 1 to 12, in particular 1 to 4, C atoms.Preferred examples include methoxy, ethoxy, n- and i-propoxy, n-, i-,sec- and ter-butoxy, pentoxy, hexoxy, heptoxy, octoxy, nonoxy anddecoxy. The alkoxy groups can be substituted by 1 to 3 halogen atoms(Cl, F), preferably: O--CF₃, O--CHF₂, O--CF₂, O--CF₂ --O, O--CF₂ --CF₂--O.

Alkylthio represents straight-chain or branched alkylthio preferablyhaving 1 to 12 C atoms. Preferred examples include methylthio,ethylthio, n- and i-propylthio, n-, i-, sec- and ter-butylthio,n-pentylthio and its isomers such as 1-, 2- and 3-methylbutylthio. Thealkylthio groups can be substituted by 1 to 3 halogen atoms (preferablychlorine and/or fluorine); preferred examples of this are di- andtrifluoromethylthio and difluorochloromethylthio.

Aralkoxy preferably contains 1 to 6 C atoms in the straight-chain orbranched alkyl moiety and preferably contains phenyl as aryl moiety.Preferred examples are benzyloxy and phenethyloxy. The aralkoxy groupscan be substituted by 1 to 3 halogen atoms (preferably chlorine and/orfluorine) or by a C₁ -C₄ -alkyl group.

Cyanoalkyl has alkyl (1 to 6) only substituted with cyano, preferablyterminally.

Hetaryl: furanyl, thienyl, thiazolyl, pyrazolyl, pyrrolyl, imidazyl,triazolyl, with or without 1 to 2 halogen or alkyl, alkoxy or thioalkoxysubstituents.

Halogen: F, Cl, Br, I.

Aralkylthio preferably contains 1 to 6 C atoms in the straight-chain orbranched alkyl moiety and preferably contains phenyl as aryl moiety. Apreferred example is benzylthio. The aralkylthio groups can besubstituted by 1 to 3 halogen atoms (preferably chlorine and/orfluorine) or by a C₁ -C₄ -alkyl group.

Aryloxy preferably contains 1 to 10 C atoms in the aryl moiety.Preferred examples are phenoxy and naphthoxy. The aryloxy groups canbear 1 to 3 substituents selected from the group consisting of halogen(preferably chlorine and/or fluorine), C₁ -C₄ -alkyl, halogeno-C₁ -C₂-alkyl (such as di- and trifluoromethyl), cyano, nitro or amino.

Arylthio preferably contains 6 to 10 C atoms in the aryl moiety.Preferred examples are phenylthio and naphthylthio. The arylthio groupscan bear the substituents listed under "aryloxy".

Preferred compounds for 1,ω-C₃ -C₆ -alk(en)ylene radicals include1,3-propylene, 1,4-butylene and 1,4-butadiene (1,3) ylene.

Compounds of the formula (I), ##STR2## in which

R¹, R², R³ denote hydrogen or methyl,

R⁴ denotes unsubstituted or substituted alkyl, cycloalkyl, alkenyl,aralkyl or aryl, are preferred.

Compounds of the formula (I), in which

R¹ denotes hydrogen,

R², R³ denote hydrogen or methyl,

R⁴ denotes unsubstituted or substituted alkyl, cycloalkyl, aralkyl oraryl, are particularly preferred.

Compounds of the formula (I), in which

R¹, R² and R³ denote hydrogen,

R⁴ denotes unsubstituted or substituted alkyl or cycloalkyl, are veryparticularly preferred.

The compounds of the invention of the formula (I) can be present asvarious (see below) tautomers, inter alia, also, in their tautomericpyrazol-5-one form.

The novel thiazolylpyrazolinone derivatives of the formula (I) areobtained by reacting thiocarbamoyl compounds of the formula (II)##STR3## in which R³ and R⁴ have the meanings given above, in thepresence or absence of a solvent or diluent and in the presence orabsence of a base, with compounds of the formula (III) ##STR4## in whichR¹ and R² have the meanings given above and X represents a leavinggroup.

The thiocarbamoyl pyrazolones of the formula (II) and the process fortheir preparation are known and are described, e.g., in JP-79/115 374,JP-79/119 031, J. Pesticide, Sci. 11, 205-212 (1986), Arch. Pharm. 316(1983) 2-6, Sci. Pharm. 51 (2) (1982) 167-172 and EP-1 515 934.

The compounds of the formula (II) are conventionally obtained byreacting corresponding α-formylacetic esters or α-formylacetamide orβ-ketoacetic esters or a β-ketoacetamide with unsubstituted orsubstituted thiosemicarbazide. The formyl acid esters to be used areobtained by various ways disclosed in the literature, thus, e.g., byanalogy with the method described in EP 417 597 or DE 2 643 205 ofhydroformylation of α,β-unsaturated esters.

The compounds of the formula (III) are likewise known or are obtainableby generally known methods.

To facilitate the ring closure reactions, bases such as sodiumhydroxide, potassium hydroxide or potassium tert-butylate areadvantageously added. Preferably, the base is added in a roughlyequivalent amount.

The processes are carried out in the presence or absence of a solvent;solvents which have proved useful are especially alcohols such asethanol or aromatic hydrocarbons such as toluene.

The processes are is carried out within a relatively broad temperaturerange. For the thiosemicarbazone formation which proceeds first,temperatures of 20° to 110° C., preferably between 60° and 90° C., areemployed. The cyclocondensation reaction which proceeds after additionof base is performed at temperatures of 20° to 100° C., preferably 20°to 40° C. The compounds of the formula (II) thus obtained are thenreacted with the compounds of the formula (III) at temperatures of -20°to 50° C., preferably 0° to 30° C.

The compounds of the formulae (I) and (II) can be isolated from thereaction mixtures by known methods. Generally, a procedure is followedin such a way that the reaction mixtures are freed of solvent and theresidue is treated with aqueous hydrochloric acid. The compoundsprecipitating out in the course of this are separated off by filteringoff with suction. However, it is also possible to pour the reactionmixture directly into a great excess of dilute hydrochloric acid and tofilter off the compounds formed as a precipitate.

The preparation of the compounds (I) of the invention is also possiblein a one-pot process without isolation of the precursor of the formula(II).

The active compounds of the formula (I) and the compositions of theinvention have a powerful microbicidal action and can be used inpractice to control undesirable microorganisms. The active compounds ofthe formula (I) and the compositions of the invention are suitable forthe protection of technical materials against attack and destruction byundesirable microorganisms.

Technical materials in the present context are to be taken to meannon-living materials which have been prepared for use in engineering.For example, technical materials which are to be protected by activecompounds of the invention against microbial change or destruction canbe adhesives, sizes, paper and board, textiles, leather, wood, coatingsand plastics, cooling lubricants and other materials which can beattacked or broken down by microorganisms. In the context of thematerials to be protected, components of production plants, for examplecooling water circuits, may also be mentioned, which can be adverselyaffected by growth of microorganisms. In the context of the presentinvention, technical materials which may be mentioned are preferablyadhesives, sizes, papers and boards, leather, wood, coatings, coolinglubricants and heat transfer fluids, particularly preferably coatings.

Microorganisms which can break down or change the technical materialsand which may be mentioned by way of example are bacteria, fungi,yeasts, algae and slime-forming organisms. Preferably, the activecompounds or compositions of the invention act against fungi, inparticular moulds, fungi which discolour and destroy wood(Basidiomycetes) and against slime-forming organisms and algae.

Microorganisms of the following genera may be mentioned by way ofexample:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puetana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

The active compounds of the formula (I) can, depending on theirrespective physical and/or chemical properties, be converted intoconventional formulations, such as solutions, emulsions, suspensions,powders, foams, pastes, granules, aerosols and dust encapsulated inpolymeric substances.

These formulations are prepared in a known manner, e.g. by mixing theactive compounds with extenders, that is liquid solvents, pressurizedliquefied gases and/or solid carriers, with or without the use ofsurface-active agents, that is emulsifiers and/or dispersants and/orfoam-forming agents. When water is used as extender, e.g., organicsolvents can also be used as cosolvents. Liquid solvents which aresuitable are essentially: aromatics, such as xylene, toluene,alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons, such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g.mineral oil fractions, alcohols, such as butanol or glycol or theirethers and esters, ketones, such as acetone, methyl ethyl ketone, methylisobutyl ketone or cyclohexanone, highly polar solvents, such asdimethylformamide or dimethyl sulphoxide, and water; liquefied gaseousextenders or carriers are taken to mean those liquids which are gaseousat room temperature and at atmospheric pressure, e.g. aerosol propellantgases, such as halogenated hydrocarbons as well as butane, propane,nitrogen and carbon dioxide; solid carriers which are useful are: e.g.natural rock flours, such as kaolins, aluminas, talcum, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth and synthetic rockflours, such as highly disperse silica, aluminium oxide and silicates;solid carriers for granules which are suitable are: e.g. crushed andfractionated natural rocks such as calcite, marble, pumice, sepiolite,dolomite and synthetic granules made of inorganic and organic flours andgranules made of organic material such as sawdust, coconut shells, corncobs and tobacco stalks; emulsifiers and/or foam-forming agents whichare suitable are: e.g. nonionogenic and anionic emulsifiers, such aspolyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers,e.g. alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates,arylsulphonates and protein hydrolysates; dispersants which are suitableare: e.g. waste ligninsulphite liquors and methylcellulose.

In the formulations, deposit builders can be used, such ascarboxymethylcellulose, natural and synthetic, pulverulent, granular orlatex-form polymers, such as gum arabic, poly(vinyl alcohol), poly(vinylacetate), and natural phospholipids, such as cephalins and lecithins andsynthetic phospholipids. Other additives can be mineral and vegetableoils.

Colorants can be used such as inorganic pigments, e.g. iron oxide,titanium oxide, Prussian blue and organic colorants can be used, such asalizarin dyes, azo dyes and metal phthalocyanin dyes and trace nutrientscan be used such as salts of iron, manganese, boron, copper, cobalt,molybdenum and zinc.

Preferably, the active compounds of the invention of the formula (I) areused to protect coatings against attack and destruction by undesirablemicroorganisms.

Coating in the present context is to be taken to mean a coat which isprepared from coating materials and is applied to a substrate. Thecoating can have penetrated into the substrate to a greater or lesserextent. It can comprise one or more layers and can be prepared byprocesses such as painting, spraying, immersion, flow coating or similarprocesses.

The compounds of the formula (I) are incorporated into the coatingmaterials or into precursors for the preparation of the coatingmaterials by conventional methods, e.g. by mixing the active compoundswith the other components.

Coating materials of the invention therefore generally contain, inaddition to at least one fungicidal active compound of the formula (I),conventional coating components in, e.g., liquid, pasty or pulverulentform, such as

colorants, such as pigments or dyes, preferably pigments. Those whichmay be mentioned by way of example are titanium dioxide, zinc oxide andiron oxide.

Binders, such as, for example, oxidatively drying alkyd resins, vinylpolymers and vinyl copolymers, acrylic polymers and acrylic copolymers,plastic powders, novolaks, amino resins, polyester resins, epoxy resins,silicone resins, isocyanate resins; preference is given to vinylpolymers and vinyl copolymers, acrylic polymers and acrylic copolymersand other binders usable in water-dilutable coating materials.

In addition, the coatings optionally contain the following additives

fillers, such as barytes, calcite, dolomite and talc,

solvents, such as alcohols, ketones, esters, glycol ethers and aliphaticand aromatic hydrocarbons,

and thickeners and thixotropes, dispersants and wetting agents,desiccants, skin-protecting agents, flow-control agents, antifoamers,corrosion inhibitors, UV-absorbers, perfumes, antistatic agents,antifreezes.

Coating materials or precursors for the preparation of coating materialswhich may be mentioned by way of example are:

sizes and adhesive based on known animal, vegetable or syntheticmaterials.

Plastic dispersions such as latex dispersions or dispersions based onother polymers.

Starch solutions, dispersions or slurries or other products made on astarch basis, such as printing thickeners.

Slurries of other raw materials such as colour pigments (e.g. iron oxidepigments, carbon black pigments, titanium dioxide pigments) or slurriesof fillers such as kaolin or calcium carbonate.

Concrete additives, for example based on molasses or lignosulphonates.

Bitumen emulsions.

Precursors and intermediates of the chemical industry, e.g. in theproduction and storage of colorants.

Inks or Indian inks.

Dispersed dyes for the coating industry.

Coats and finishes.

The activity and the action spectrum of the active compounds of theformula (I) or the compositions, precursors or quite generallyformulations which can be prepared therefrom can be enhanced if otherantimicrobially active compounds, fungicides, bactericides, insecticidesor other active compounds for enlarging the action spectrum or toachieve particular effects such as additional protection against insectsare optionally added. These mixtures can have a broader action spectrumthan the compounds of the invention.

In many cases synergistic effects are increased by these means, i.e. theactivity of the mixture is greater than the activity of the individualcomponents. Particularly expedient mixing partners are, e.g., thefollowing compounds:

Triazoles, such as:

amitrole, azocyclotin, BAS 480F, bitertanol, difenoconazole,fenbuconazole, fenchlorazole, fenethanil, fluquinconazole, flusilazole,flutriafol, imibenconazole, isozofos, myclobutanil, metconazole,epoxyconazole, paclobutrazol, penconazole, propioconazole,(±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,tetraconazole, triadimefon, triadimenol, triapenthenol, triflumizole,triticonazole, uniconazole and their metal salts and acid adducts.

Imidazoles such as:

imazalil, perfurazoate, prochloraz, triflumizole,2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,thiazolecarboxanilides, such as2',6'-dibromo-2-methyl-4-trifluoromethoxy-4'-trifluoromethyl-1,3-thiazole-5-carboxanilide,1-imidazolyl-1-(4'-chlorophenoxy)-3,3-dimethylbutan-2-one and theirmetal salts and acid adducts.

Methyl (E)-2- 2-6-(2-cyanophenoxy)pyrimidin-4-yloxy!phenyl!3-methoxyacrylate, methyl(E)-2- 2-6-(2-thioamidophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate,methyl (E)-2- 2-6-(2-fluorophenoxy)pyrimidine-4-yloxy!phenyl!-3-methoxyacrylate, methyl(E)-2- 2-6-(2,6-difluorophenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate,methyl (E)-2- 2- 3-(pyrimidin-2-yloxy)phenoxy!phenyl!-3-methoxyacrylate,methyl (E)-2- 2-3-(5-methylpyrimidin-2-yloxy)-phenoxy!phenyl!-3-methoxyacrylate, methyl(E)-2- 2- 3-(phenylsulphonyloxy)phenoxy!phenyl!-3-methoxyacrylate,methyl (E)-2- 2- 3-(4-nitrophenoxy)phenoxy!phenyl!-3-methoxyacrylate,methyl (E)-2- 2-phenoxyphenyl!-3-methoxyacrylate, methyl (E)-2-2-(3,5-dimethylbenzoyl)pyrrol-1-yl!-3-methoxyacrylate, methyl (E)-2-2-(3-methoxyphenoxy)phenyl!-3-methoxyacrylate, methyl (E)-2-2-(2-phenylethylen-1-yl)-phenyl!-3-methoxyacrylate, methyl (E)-2-2-(3,5-dichlorophenoxy)pyridin-3-yl!-3-methoxyacrylate, methyl(E)-2-(2-(3-(1,1,2,2-tetrafluoroethoxy)phenoxy)phenyl)-3-methoxyacrylate,methyl (E)-2-(2-3-(alpha-hydroxybenzyl)phenoxy!phenyl)-3-methoxyacrylate, methyl(E)-2-(2-(4-phenoxypyridin-2-yloxy)phenyl)-3-methoxyacrylate, methyl(E)-2- 2-(3-n-propyloxyphenoxy)phenyl!3-methoxyacrylate, methyl (E)-2-2-(3-isopropyloxyphenoxy)phenyl!-3-methoxyacrylate, methyl (E)-2- 2-3-(2-fluorophenoxy)pehnoxy!phenyl!-3-methoxyacrylate, methyl (E)-2-2-(3-ethoxyphenoxy)phenyl!-3-methoxyacrylate, methyl (E)-2-2-(4-tert-butylpyridin-2-yloxy)phenyl!-3-methoxyacrylate, methyl (E)-2-2- 3-(3-cyanophenoxy)phenoxy!phenyl!-3-methoxyacrylate, methyl (E)-2-2-(3-methhylpyridin-2-yloxymethhyl)phenyl!-3-methoxyacrylate, methyl(E)-2- 2-6-(2-methylphenoxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate, methyl(E)-2- 2-(5-bromopyridin-2-yloxy-methyl)phenyl!-3-methoxyacrylate,methyl (E)-2-2-(3-(3-iodopyridin-2-yloxy)phenoxy)phenyl!-3-methoxyacrylate, methyl(E)-2- 2-6-(2-chloropyridin-3-yloxy)pyrimidin-4-yloxy!phenyl!-3-methoxyacrylate,(E),(E)methyl 2-2-(5,6-dimethylpyrazin-2-ylmethyloximinomethyl)phenyl!-3-methoxyacrylate,(E)-methyl 2-{2-6-(6-methylpyridin-2-yloxy)pyrimidin-4-yloxy!phenyl}-3-methoxyacrylate,(E),(E)-methyl2-{2-(3-methoxyphenyl)methyloximinomethyl!phenyl}-3-methoxyacrylate,(E)methyl2-{2-(6-(2-azidophenoxy)pyrimidin-4-yloxy!phenyl}-3-methoxyacrylate,(E),(E)methyl 2-{2-6-phenylpyrimidin-4-yl)-methoximinomethyl!phenyl}-3-methoxyacrylate,(E),(E)methyl 2-{2-(4-chlorophenyl)-methyloximinomethyl!phenyl}-3-methoxyacrylate,(E)methyl 2-{2-6-(2-n-propylphenoxy)-1,3,5-triazin-4-yloxy!phenyl}-3-methoxyacrylate,(E),(E)methyl 2-{2-(3-nitrophenyl)methyloximinomethyl!phenyl}-3-methoxyacrylate;

Succinate dehydrogenase inhibitors such as:

fenfuram, furcarbanil, cyclafluramid, furmecyclox, Seedvax, metsulfovax,pyrocarbolid, oxycarboxin, shirlan, mebenil (mepronil), benodanil,flutolanil (Moncut); naphthalene derivates such as terbinafine,naftifine, butenafine,3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);

Sulphenamides such as dichlofluanid, tolylfluanid, folpet, fluorfolpet;captan, captofol; benzimidazoles such as carbendazim, benomyl,furathiocarb, fuberidazole, thiophonatmethyl, thiabendazole or theirsalts;

morpholine derivatives such as tridemorph, fenpropimorph, falimorph,dimethomorph, dodemorph, aldimorph, fenpropidin and their arylsulphonicsalts, such as p-toluene-sulphonic acid and p-dodecylphenyl-sulphonicacid;

dithiocarbamates, cufraneb, ferbam, mancopper, mancozeb, maneb, metam,metiram, thiram zeneb, ziram;

benzothiazoles such as 2-mercaptobenzothiazole;

benzamides such as 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide;

boron compounds such as boric acid, boric esters, borax;

formaldehyde and compounds eliminating formaldehyde such as benzylalcohol mono(poly)hemiformal, oxazolidines, hexa-hydro-S-triazines,N-methylol chloracetamide, paraformadehyde, nitropyrin, oxolinic acid,tecloftalam;

tris-N-(cyclhexyldiazeniumdioxy)-aluminium,N-(cyclo-hexyldiazeniumdioxy)-tributyl-tinor K salts, bis-N-cyclohexyldiazeniumdioxy)-copper;

N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-on,4,5-dichloro-N-octyl-isothiazolin-3-one, N-octyl-isothiazolin-3-one,4,5-trimethylene-isothiazolinones, 4,5-benzisothiazolinones, N-methylolchloracetamide;

aldehydes such as cinnamaldehyde, formaldehyde, glutaric dialdehyde,β-bromo-cinnamaldehyde;

thiocyanates such as thiocyanatomethylthiobenzothiazole,methylenebisthiocyanate, etc.;

quaternary ammonium compounds such as benzyldimethyltetradecylammoniumchloride, benzyldimethyldodecylammonium chloride,didecyldimethaylammonium chloride; iodine derivatives, such asdiiodomethyl-p-tolylsulphone, 3-iodo-2-propinyl alcohol,4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallyl alcohol,3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate, 3-iodo-2-propinylcyclohexylcarbamate, 3-iodo-2-propinyl phenylcarbamate;

phenol derivatives, such as tribromophenol, tetrachlorophenol,3-methyl-4-chlorophenol, 3,5-dimethyl-4-chlorophenol, phenoxyethanol,dichlorophen, o-phenylphenol, m-phenylphenol, p-phenylphenol,2-benzyl-4-chlorophenol and their alkali metal salts and earth metalsalts;

microbicides having an activated halogen group such as chloroacetamide,bronopol, bronidox, tectamers such as 2-bromo-2-nitro-1,3-propanediol,2-bromo-4'-hydroxy-acetophenone, 2,2-dibromo-3-nitrile-propionamide,1,2-dibromo-2,4-dicyanobutan, β-bromo-β-nitrostyrene;

pyridines, such as 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn andZn salts), tetrachloro-4-methylsulphonylpyridine, pyrimethanol,mepanipyrim, dipyrithion,1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl)-2(1H)-pyridin;

metal soaps, such as tin naphthenate, copper naphthenate, zincnaphthenate, tin octoate, copper octoate, zinc octoate, tin2-ethylhexanoate, copper 2-ethylhexanoate, zinc 2-ethylhexanoate, tinoleate, copper oleate, zinc oleate, tin phosphate, copper phosphate,zinc phosphate, tin benzoate, copper benzoate and zinc benzoate;

metal salts, such as copper hydroxycarbonate, sodium dichromate,potassium dichromate, potassium chromate, copper sulphate, copperchloride, copper borate, zinc fluorosilicate, copper fluorosilicate;

oxides, such as tributyltin oxide, Cu₂ O, CuO, ZnO;

dialkyldithiocarbamates, such as Na and Zn salts ofdialkyldithiocarbamates, tetramethylthiuram disulphide, potassiumN-methyl-dithiocarbamate;

nitriles such as 2,4,5,6-tetrachloroisophthalodinitrile, disodiumcyano-dithioimidocarbamate;

quinolines, such as 8-hydroxyquinolin and their Cu salts;

mucochloric acid, 5-hydroxy-2(5H)-furanone;

4,5-dichlorodithiazolinone, 4,5-benzodithiazolinone,4,5-trimethylenedithiazolinone, 4,5-dichloro-(3H)-1,2-dithiol-3-one,3,5-dimethyl-tetrahydro-1,3,5-thiadiazin-2-thione,N-(2-p-chlorobenzoylethyl)-hexaminium chloride, potassiumN-hydroxymethyl-N'-methyl-dithiocarbamate,

2-oxo-2-(4-hydroxy-phenyl)acetohydroxycinnamoyl chloride, phenyl2-chlorocyanovinyl sulphone, phenyl 1,2-dichloro-2-cyano-vinyl sulphone;

Ag, Zn or Cu-containing zeolites, alone or incorporated into polymericmaterial.

Very particular preference is given to mixtures containing azaconazole,bromuconazole, cyproconazole, dichlobutrazol, diniconazole,hexaconazole, metconazole, penconazole, propiconazole, tebuconazole,methyl (E)-methoximino α-(o-tolyloxy)-o-tolyl)!-acetate, methyl(E)-2-{2-6-(2-cyanophenoxy)-pyrimidin-4-yl-oxy!phenyl}-3-methoxyacrylate,methfuroxam, carboxin, fenpiclonil,4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile,butenafine, imazalil, N-methyl-isothiazolin-3-one,5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one,benzisothiazolinone, N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol(hemi)-formal, glutaraldehyde, omadine, dimethyl dicarbonate, and/or3-iodo-2-propinyl n-butylcarbamate.

Furthermore, highly active mixtures are also prepared containing thefollowing active compounds:

Fungicides:

acypetacs, 2-aminobutane, ampropylfos, anilazine, benalaxyl, bupirimate,chinomethionate, chloroneb, chlozolinate, cymoxanil, dazomet,diclomezine, dichloram, diethofencarb, dimethirimol, diocab, dithianone,dodine, drazoxolon, edifenphos, ethirimol, etridiazole, fenarimol,fenitropan, fentin acetate, fentin hydroxide, ferimzone, fluazinam,fluromide, flusulphamide, flutriafol, fosetyl, fthalide, furalaxyl,guazatine, hymexazol, iprobenfos, iprodione, isoprothiolane, metalaxyl,ethasulfocarb, nitrothal-isopropyl, nuarimol, ofurace, oxadiyl,perfluorazoate, pencycuron, phosdiphen, pimaricin, piperalin,procymidone, propamocarb, propineb, pyrazophos, pyrifenox, pyroquilone,quintozene, tar oils, tecnazene, thicyofen, thiophanate-methyl,tolclofos-methyl, triazoxide, trichlamide, tricyclazole, triforine,vinclozolin.

Insecticides:

phosphoric esters, such as azinphos-ethyl, azinphos-methyl,α-1(4-chlorophenyl)-4-(O-ethyl, S-propyl)phosphoryloxy-pyrazole,chlorpyrifos, coumaphos, demeton, demeton-S-methyl, diazinon,dichlorvos, dimethoate, ethoate, ethoprophos, etrimfos, fenitrothion,fenthion, heptenophas, parathion, parathion-methyl, phosalone, phoxim,pirimiphos-ethyl, pirimiphos-methyl, profenofos, prothiofos, sulfprofos,triazophos and trichlorphon;

carbamates, such as aldicarb, bendiocarb,α-2-(1-methylpropyl)phenylmethylcarbamate, butocarboxim, butoxycarboxim,carbaryl, carbofuran, carbosulfan, cloethocarb, isoprocarb, methomyl,oxamyl, pirimicarb, promecarb, propoxur and thiodicarb;

organosilicon compounds, preferably dimethyl(phenyl)silyl-methyl3-phenoxybenzyl ethers, such as dimethyl-(4-ethoxyphenyl)-silylmethyl3-phenoxybenzyl ether or (dimethylphenyl)-silyl-methyl2-phenoxy-6-pyridylmethyl ethers, such asdimethyl-(9-ethoxy-phenyl)-silylmethyl 2-phenoxy-6-pyridylmethyl etheror (phenyl)-3-(3-phenoxyphenyl)-propyl!(dimethyl)-silanes, such as(4-ethoxyphenyl)- 3-(4-fluoro-3-phenoxyphenyl-propyl!dimethylsilane,silafluofen;

pyrethroids such as allethrin, alphamethrin, bioresmethrin, byfenthrin,cycloprothrin, cyfluthrin, decamethrin, cyhalothrin, cypermethrin,deltamethrin, alpha-cyano-3-phenyl2-methylbenzyl-2,2-dimethyl-3-(2-chloro-2-trifluoro-methylvinyl)cyclopropanecarboxylate,fenpropathrin, fenfluthrin, fenvalerate, flucythrinate, flumethrin,fluvalinate, permethrin, resmethrin and tralomethrin;

nitroimines and nitromethylenes, such as 1-(6-chloro-3-pyridinyl)-methyl!-4,5-dihydro-N-nitro-1H-imidazol-2-amine(imidacloprid),N- (6-chloro-3-pyridyl)methyl-!N² -cyano-N¹ -methylacetamide (NI-25);

abamectin, AC 303, 630, acephate, acrinathrin, alanycarb, aldoxycarb,aldrin, amitraz, azamethiphos, Bacillus thuringiensis, phosmet,phosphamidon, phosphine, prallethrin, propaphos, propetamphos,prothoate, pyraclofos, pyrethrins, pyridaben, pyridafenthion,pyriproxyfen, quinalphos, RH-7988, rotenone, sodium fluoride, sodiumhexafluorosilicate, sulfotep, sulfuryl fluoride, tar oils,teflubenzuron, tefluthrin, temephos, terbufos, tetrachlorvinphos,tetramethrin, O-2-tert-butyl-pyrimidin-5-yl o-isopropylphosphorothiate,thiocyclam, thiofanox, thiometon, tralomethrin, triflumuron,trimethacarb, vamidothion, Verticillium lacanii, XMC, xylylcarb,benfuracarb, bensultap, bifenthrin, bioallethrin, MERbioallethrin(S)-cyclopentenyl isomer, bromophos, bromophos-ethyl, buprofezin,cadusafos, calcium polysulfide, carbophenothion, cartap,quinomethionate, chlordane, chlorfenvinphos, chlorfluazuron,chlormephos, chloropicrin, chlorpyrifos, cyanophos, beta-cyfluthrin,alpha-cypermethrin, cyophenothrin, cyromazine, dazomet, DDT,demeton-S-methylsulphone, diafenthiuron, dialifos, dicrotophos,diflubenzuron, dinoseb, deoxabenzofos, diaxacarb, disulfoton, DNOC,empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion,etofenprox, fenobucarb, fenoxycarb, fensulfothion, fipronil,flucycloxuron, flufenprox, flufenoxuron, fonofos, formetanate,formothion, fosmethilan, furathiocarb, heptachlor, hexaflumuron,hydramethylnon, hydrogen cyanide, hydroprene, IPSP, isazofos,isofenphos, isoprothiolane, isoxathion, iodfenphos, kadethrin, lindane,malathion, mecarbam, mephosfolan, mercurous, chloride, metam,metarthizium, anisopliae, methacrifos, methamidophos, methidiathon,methiocarb, methoprene, methoxychlor, methyl isothiocyanate, metholcarb,mevinphos, monocrotophos, naled, neodiprion sertifer NPV, nicotine,omethoate, oxydemeton-methyl, pentachlorophenol, petroleum oils,phenothrin, phenthoate, phorate;

Molluscicides:

fentinacetate, metaldehyde, methiocarb, niclosamide, thiodicarb,trimethacarb.

Algicides:

copper sulphate, dichlororphen, endothal, fentinacetate, quinoclamine.

Herbicides:

acetochlor, acifluorfen, aclonifen, acrolein, alachlor, alloxydim,ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulamatrazine, aziptrotryne, benazolin, benfluralin, benfuresate,bensulfuron, bensulfide, bentazone, benzofencap, benzthiazuron, bifenox,bilanafos, borax, dichlorprop, dichlorprop-P, diclofop, diethatyl,difenoxuron, difenzoquat, diflufenican, dimefinon, dimepiperate,dimethachlor, dimethametryn, dimethipin, dimethylarsinic acid,dinitramine, dinoseb, dinoseb, dinoseb acetate, dinoseb, bromacil,bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos, fuenachlor,butralin, butylate, carbetamide, CGA 184927, chlormethoxyfen,chloramben, chlorbromuron, chlorbutam, chlorfurenol, chloridazon,chlorimuron, chlornitrofen, chloroacetic acid, achloropicrin,chlorotoluron, chloroxuron, chlorprepham, chlorsulfuron, chlorthal,chlorthiamid, cinmethylin, cinofulsuron, clethodim, clomazone,clomeprop, clopyralid, cyanamide, cyanazine, dinoseb acetate, dinoterb,diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC, PPX-A 788,DPX-E96361, DSMA, eglinazine, endothal, EPTC, esprocarb, ethalfluralin,ethidimuron, ethofumesate, fenoxaprop, fenoxaprop-P, fenuron, flamprop,flamprop-M, flazasulfuron, fluazifop, fluazifop-P, fluchloralin,flumeturon, fluorocgycofen, fluoronitrofen, flupropanate, flurenol,fluridone, flurochloridone, fluoroxypyr, cycloate, cycloxydim, 2,4-D,daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn, dicamba,dichlorbenil, isoproturon, isouron, isoxaben, isoxapyrifop, lactofen,lenacil, linuron, LS830556, MCPA, MCPA-thioethyl, MCPB, mecoprop,mecoprop-P, mefenacet, mefluidide, metam, metamitron, metazachlor,methabenzthiazuron, methazole, methoproptryne, methyldymron, methylisothiocyanate, metobromuron, fomosafen, fosamine, furyloxyfen,glufosinate, glyphosate, haloxyfop, hexazinone, imazamethabenz,imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, propyzamide,prosulfocab, pyrazolynate, pyrazolsulfuron, pyrazoxyfen, pyributicarb,pyridate, quinclorac, quiumerac, quinocloamine, quizalofop,quzizalofop-P, S-23121, sethoxydim, sifuron, simazine, simetryn, SMY1500, sodium chlorate, sulfometuron, tar oils, TCA, metolachlor,metoxuron, metribzin, metsulfuron, molinate, monoalide, monolinuron,MSMA, naproanilide, napropamide, naptalam, neburon, nicosulfuron,nipyraclofen, norflurazon, orbencarb, oaryzalin, oxadiazon, oxyfluorfen,paraquat, pebulate, pendimethalin, pentachlorophenol, pentaochlor,petroleum oils, phenmedipham, picloram, piperophos, pretilachlor,primisulfuron, prodiamine, proglinazine, propmeton, prometryn,propachlor, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine,terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil,tioclorim, tralkoxydim, tri-allate, triasulfuron, tribenzuron,triclopyr, tridiphane, trietazine, trifluralin, IBI-C4874 vernolate,propanil, propaquizafop, propazine, propham.

The weight ratios of the active compounds in these active compoundcombinations can be varied in relatively large ranges.

Preferably, the active compound combinations contain the active compoundat 0.1 to 99.9%, in particular at 1 to 75%, particularly preferably 5 to50%, the remainder up to 100% being made up by one or more of theabovementioned mixing partners.

The microbicidal compositions or concentrates used to protect thetechnical materials contain the active compound or the active compoundcombination at a concentration of 0.01 and 95% by weight, in particular0.1 to 60% by weight.

The application concentrations of the active compound to be used or ofthe active compound combination to be used depend on the type andoccurrence of the microorganisms to be controlled and on the compositionof the material to be protected. The optimal usage rate can bedetermined by test strips.

Generally, the application concentrations are in the range from 0.001 to5% by weight, preferably from 0.05 to 1.0% by weight, based on thematerial to be protected.

The active compounds or compositions of the invention enable, in anadvantageous manner, the microbicidal compositions available to date tobe replaced by more effective ones. They show good stability andadvantageously have a broad action spectrum.

The following examples serve to illustrate the invention. The inventionis not restricted to the examples.

PREPARATION EXAMPLES Example 1 (Precursor of the Formula (II))

10.3 g (0.06 mol) of ethyl α-formyl-hexanoate and 5.5 g (0.06 mol): ofthiosemicarbazide are introduced into 200 ml of ethanol and stirred for3 hours at 80° C.

The mixture is then brought to room temperature and 6.9 g of potassiumtert-butoxide are added with stirring, in order to stir the mixture fora further 4 hours at room temperature. The contents of the flask arethen stirred into a mixture of 800 ml of water and 50 ml of concentratedhydrochloric acid and the resulting precipitate is filtered off bysuction. After thorough washing with water, the product is left in thedrying cabinet until constant weight. The compound can be purified byrecrystallization from ethanol.

Yield: 9.4 g (80.3% of theory)

m.p.: 139°-141° C.

(Final Stage of Formula (I))

26.48 g (0.236 mol) of potassium tert-butoxide are added to 47.1 g(0.236 mol) of the precursor in 450 ml of tetrahydrofuran at 25° C.After cooling to 0° C., 30 ml of 50% chloroacetaldehyde are addeddropwise and the mixture is stirred for 16 hours at 25° C. After pouringthe mixture into 750 ml of 10% HCl, it is extracted with methylenechloride, dried, the solvent is evaporated and the residue is stirredwith diisopropyl ether.

26.1 g of the target compound I/007 of melting point 89°-91° C. areobtained. Recrystallization maintains the melting point at 91° C.

The following compounds of the formula (I) are obtained by analogy withExample 1 and in accordance with the general descriptions, it being alsopossible here to prepare the workup of the precursor directly and toprepare the final stage economizing on base:

                  TABLE 1                                                         ______________________________________                                        R.sup.1 = R.sup.2 = R.sup.3 = H                                               Example No.                                                                            R.sup.4             m.p.                                             ______________________________________                                        1        H                                                                    2        Me                                                                   3        Et                                                                   4        n-Pr                                                                 5        i-Pr                                                                 6        c-Pr                                                                 7        n-Bu                91° C.                                    8        i-Bu                                                                 9        s-Bu                                                                 10       t-Bu                                                                 11       n-C.sub.5 H.sub.4                                                    12                                                                                      ##STR5##                                                            13                                                                                      ##STR6##                                                            14                                                                                      ##STR7##                                                            15                                                                                      ##STR8##                                                            16                                                                                      ##STR9##                                                            17                                                                                      ##STR10##                                                           18                                                                                      ##STR11##                                                           19                                                                                      ##STR12##                                                           20                                                                                      ##STR13##                                                           21                                                                                      ##STR14##                                                           22                                                                                      ##STR15##                                                           23                                                                                      ##STR16##                                                           24                                                                                      ##STR17##                                                           25                                                                                      ##STR18##                                                           26                                                                                      ##STR19##                                                           27                                                                                      ##STR20##                                                           28                                                                                      ##STR21##                                                           29                                                                                      ##STR22##                                                           30                                                                                      ##STR23##                                                           31                                                                                      ##STR24##                                                           32                                                                                      ##STR25##                                                           33                                                                                      ##STR26##                                                           34                                                                                      ##STR27##                                                           35       NCCH.sub.2CH.sub.2                                                   36       CF.sub.3                                                             37       CF.sub.3CF.sub.2                                                     38       CF.sub.3CF.sub.2CF.sub.2                                             39       CF.sub.2CF.sub.2CH.sub.2                                             40       CF.sub.3CF.sub.2CF.sub.2CH.sub.2                                     41                                                                                      ##STR28##          134-135° C.                               42                                                                                      ##STR29##                                                           43                                                                                      ##STR30##                                                           44                                                                                      ##STR31##                                                           45                                                                                      ##STR32##                                                           46                                                                                      ##STR33##                                                           47                                                                                      ##STR34##                                                           48                                                                                      ##STR35##                                                           49                                                                                      ##STR36##                                                           50                                                                                      ##STR37##                                                           51                                                                                      ##STR38##                                                           52                                                                                      ##STR39##                                                           53                                                                                      ##STR40##                                                           54                                                                                      ##STR41##                                                           55                                                                                      ##STR42##                                                           56                                                                                      ##STR43##                                                           57                                                                                      ##STR44##                                                           58                                                                                      ##STR45##                                                           59                                                                                      ##STR46##                                                           60                                                                                      ##STR47##                                                           61                                                                                      ##STR48##                                                           62                                                                                      ##STR49##                                                           63                                                                                      ##STR50##                                                           64                                                                                      ##STR51##                                                           65                                                                                      ##STR52##                                                           66                                                                                      ##STR53##                                                           67                                                                                      ##STR54##                                                           68                                                                                      ##STR55##                                                           69                                                                                      ##STR56##                                                           70                                                                                      ##STR57##                                                           71                                                                                      ##STR58##                                                           72                                                                                      ##STR59##                                                           73                                                                                      ##STR60##                                                           74                                                                                      ##STR61##                                                           75                                                                                      ##STR62##                                                           76                                                                                      ##STR63##                                                           77                                                                                      ##STR64##                                                           78       n-C.sub.7 H.sub.15                                                   79       n-C.sub.8 H.sub.17                                                   80       n-C.sub.9 H.sub.19                                                   81       n-C.sub.10H.sub.21                                                   82       n-C.sub.11 H.sub.23                                                  83       n-C.sub.12 H.sub.25                                                  84       n-C.sub.13 H.sub.27                                                  85                                                                                      ##STR65##                                                           86                                                                                      ##STR66##                                                           87                                                                                      ##STR67##                                                           88                                                                                      ##STR68##                                                           89                                                                                      ##STR69##                                                           90                                                                                      ##STR70##                                                           91                                                                                      ##STR71##                                                           92                                                                                      ##STR72##                                                           93                                                                                      ##STR73##                                                           94                                                                                      ##STR74##                                                           95                                                                                      ##STR75##                                                           96                                                                                      ##STR76##                                                           97                                                                                      ##STR77##                                                           98                                                                                      ##STR78##                                                           99                                                                                      ##STR79##                                                           100                                                                                     ##STR80##                                                           101                                                                                     ##STR81##                                                           102                                                                                     ##STR82##                                                           103                                                                                     ##STR83##                                                           104                                                                                     ##STR84##                                                           105                                                                                     ##STR85##                                                           106                                                                                     ##STR86##                                                           107                                                                                     ##STR87##                                                           108                                                                                     ##STR88##                                                           109                                                                                     ##STR89##                                                           110                                                                                     ##STR90##                                                           111                                                                                     ##STR91##                                                           112                                                                                     ##STR92##                                                           113                                                                                     ##STR93##                                                           114                                                                                     ##STR94##                                                           115                                                                                     ##STR95##                                                           116                                                                                     ##STR96##                                                           117                                                                                     ##STR97##                                                           118                                                                                     ##STR98##                                                           119                                                                                     ##STR99##                                                           120                                                                                     ##STR100##                                                          121                                                                                     ##STR101##                                                          122                                                                                     ##STR102##                                                          123                                                                                     ##STR103##                                                          124                                                                                     ##STR104##                                                          125                                                                                     ##STR105##                                                          126                                                                                     ##STR106##                                                          127                                                                                     ##STR107##                                                          128                                                                                     ##STR108##                                                          129                                                                                     ##STR109##                                                          130                                                                                     ##STR110##                                                          131                                                                                     ##STR111##                                                          132                                                                                     ##STR112##                                                          133                                                                                     ##STR113##                                                          134                                                                                     ##STR114##                                                          135                                                                                     ##STR115##                                                          136                                                                                     ##STR116##                                                          137                                                                                     ##STR117##                                                          138                                                                                     ##STR118##                                                          139                                                                                     ##STR119##                                                          140                                                                                     ##STR120##                                                          141                                                                                     ##STR121##                                                          142                                                                                     ##STR122##                                                          143                                                                                     ##STR123##                                                          144                                                                                     ##STR124##                                                          145                                                                                     ##STR125##                                                          146                                                                                     ##STR126##                                                          147                                                                                     ##STR127##                                                          148                                                                                     ##STR128##                                                          149                                                                                     ##STR129##                                                          150                                                                                     ##STR130##                                                          151                                                                                     ##STR131##                                                          152                                                                                     ##STR132##                                                          153                                                                                     ##STR133##                                                          154                                                                                     ##STR134##                                                          155                                                                                     ##STR135##                                                          156                                                                                     ##STR136##                                                          157                                                                                     ##STR137##                                                          158                                                                                     ##STR138##                                                          159                                                                                     ##STR139##                                                          160                                                                                     ##STR140##                                                          161                                                                                     ##STR141##                                                          162                                                                                     ##STR142##                                                          163      MeO                                                                  164      EtO                                                                  165      n-PrO                                                                166      n-BuO                                                                167      MeSCH.sub.2                                                          168      EtSCH.sub.2                                                          169      n-PrSCH.sub.2                                                        170      n-BuSCH.sub.2                                                        171      i-PrSCH.sub.2                                                        172      n-C.sub.5 H.sub.4SCH.sub.2                                           173      MeS(CH.sub.2).sub.2                                                  174      EtS(CH.sub.2).sub.2                                                  175      n-PrS(CH.sub.2).sub.2                                                176      n-BuS(CH.sub.2).sub.2                                                177      MeOCH.sub.2                                                          178      EtOCH.sub.2                                                          179      n-PrOCH.sub.2                                                        180      n-BuOCH.sub.2                                                        181      N-PrOCH.sub.2                                                        182      n-C.sub.5 H.sub.4OCH.sub.2                                           183      MeO(CH.sub.2).sub.2                                                  184      EtO(CH.sub.2).sub.2                                                  185      n-PrO(CH.sub.2).sub.2                                                186      n-BuO(CH.sub.2).sub.2                                                187      PhSCH.sub.2                                                          188      PhOCH.sub.2                                                          189      PhCH.sub.2SCH.sub.2                                                  190      PHCH.sub.2 OCH.sub.2                                                 191                                                                                     ##STR143##                                                          192                                                                                     ##STR144##                                                          193                                                                                     ##STR145##                                                          194                                                                                     ##STR146##                                                          195                                                                                     ##STR147##                                                          196                                                                                     ##STR148##                                                          197                                                                                     ##STR149##                                                          198                                                                                     ##STR150##                                                          199                                                                                     ##STR151##                                                          200                                                                                     ##STR152##                                                          201                                                                                     ##STR153##                                                          202                                                                                     ##STR154##                                                          203                                                                                     ##STR155##                                                          204                                                                                     ##STR156##                                                          205      n-C.sub.17H.sub.39                                                   ______________________________________                                    

                  TABLE II                                                        ______________________________________                                        R.sup.1 = R.sup.3 = H, R.sup.2 = Me                                           Example No.                                                                            R.sup.4             m.p.                                             ______________________________________                                        206      H                                                                    207      Me                                                                   208      Et                                                                   209      n-Pr                                                                 210      i-Pr                                                                 211      c-Pr                                                                 212      n-Bu                                                                 213      i-Bu                                                                 214      s-Bu                                                                 215      t-Bu                                                                 216      n-C.sub.5 H.sub.4                                                    217                                                                                     ##STR157##                                                          218                                                                                     ##STR158##                                                          219                                                                                     ##STR159##                                                          220                                                                                     ##STR160##                                                          221                                                                                     ##STR161##                                                          222                                                                                     ##STR162##                                                          223                                                                                     ##STR163##                                                          24                                                                                      ##STR164##                                                          225                                                                                     ##STR165##                                                          226                                                                                     ##STR166##                                                          227                                                                                     ##STR167##                                                          228                                                                                     ##STR168##                                                          229                                                                                     ##STR169##                                                          230                                                                                     ##STR170##                                                          231                                                                                     ##STR171##                                                          232                                                                                     ##STR172##                                                          233                                                                                     ##STR173##                                                          234                                                                                     ##STR174##                                                          235                                                                                     ##STR175##                                                          236                                                                                     ##STR176##                                                          237                                                                                     ##STR177##                                                          238                                                                                     ##STR178##                                                          239                                                                                     ##STR179##                                                          240      NCCH.sub.2CH.sub.2                                                   241      CF.sub.3                                                             242      CF.sub.3CF.sub.2                                                     243      CF.sub.3CF.sub.2CF.sub.2                                             244      CF.sub.2CF.sub.2CH.sub.2                                             245      CF.sub.3CF.sub.2CF.sub.2CH.sub.2                                     246                                                                                     ##STR180##                                                          247                                                                                     ##STR181##                                                          248                                                                                     ##STR182##                                                          249                                                                                     ##STR183##                                                          250                                                                                     ##STR184##                                                          251                                                                                     ##STR185##                                                          252                                                                                     ##STR186##                                                          253                                                                                     ##STR187##                                                          254                                                                                     ##STR188##                                                          255                                                                                     ##STR189##                                                          256                                                                                     ##STR190##                                                          257                                                                                     ##STR191##                                                          258                                                                                     ##STR192##                                                          259                                                                                     ##STR193##                                                          260                                                                                     ##STR194##                                                          261                                                                                     ##STR195##                                                          262                                                                                     ##STR196##                                                          263                                                                                     ##STR197##                                                          264                                                                                     ##STR198##                                                          265                                                                                     ##STR199##                                                          266                                                                                     ##STR200##                                                          267                                                                                     ##STR201##                                                          268                                                                                     ##STR202##                                                          269                                                                                     ##STR203##                                                          270                                                                                     ##STR204##                                                          271                                                                                     ##STR205##                                                          272                                                                                     ##STR206##                                                          273                                                                                     ##STR207##                                                          274                                                                                     ##STR208##                                                          275                                                                                     ##STR209##                                                          276                                                                                     ##STR210##                                                          277                                                                                     ##STR211##                                                          278                                                                                     ##STR212##                                                          279                                                                                     ##STR213##                                                          280                                                                                     ##STR214##                                                          281                                                                                     ##STR215##                                                          282                                                                                     ##STR216##                                                          283      n-C.sub.7 H.sub.15                                                   284      n-C.sub.8 H.sub.17                                                   285      n-C.sub.9 H.sub.19                                                   286      n-C.sub.10H.sub.21                                                   287      n-C.sub.11 H.sub.23                                                  288      n-C.sub.12 H.sub.25                                                  289      n-C.sub.13 H.sub.27                                                  290                                                                                     ##STR217##                                                          291                                                                                     ##STR218##                                                          292                                                                                     ##STR219##                                                          293                                                                                     ##STR220##                                                          294                                                                                     ##STR221##                                                          295                                                                                     ##STR222##                                                          296                                                                                     ##STR223##                                                          297                                                                                     ##STR224##                                                          298                                                                                     ##STR225##                                                          299                                                                                     ##STR226##                                                          300                                                                                     ##STR227##                                                          301                                                                                     ##STR228##         oil                                              302                                                                                     ##STR229##                                                          303                                                                                     ##STR230##                                                          304                                                                                     ##STR231##                                                          305                                                                                     ##STR232##                                                          306                                                                                     ##STR233##                                                          307                                                                                     ##STR234##                                                          308                                                                                     ##STR235##                                                          309                                                                                     ##STR236##                                                          310                                                                                     ##STR237##                                                          311                                                                                     ##STR238##                                                          312                                                                                     ##STR239##                                                          313                                                                                     ##STR240##                                                          314                                                                                     ##STR241##                                                          315                                                                                     ##STR242##                                                          316                                                                                     ##STR243##                                                          317                                                                                     ##STR244##                                                          318                                                                                     ##STR245##                                                          319                                                                                     ##STR246##                                                          320                                                                                     ##STR247##                                                          321                                                                                     ##STR248##                                                          322                                                                                     ##STR249##                                                          323                                                                                     ##STR250##                                                          324                                                                                     ##STR251##                                                          325                                                                                     ##STR252##                                                          326                                                                                     ##STR253##                                                          327                                                                                     ##STR254##                                                          328                                                                                     ##STR255##                                                          329                                                                                     ##STR256##                                                          330                                                                                     ##STR257##                                                          331                                                                                     ##STR258##                                                          332                                                                                     ##STR259##                                                          333                                                                                     ##STR260##                                                          334                                                                                     ##STR261##                                                          335                                                                                     ##STR262##                                                          336                                                                                     ##STR263##                                                          337                                                                                     ##STR264##                                                          338                                                                                     ##STR265##                                                          339                                                                                     ##STR266##                                                          340                                                                                     ##STR267##                                                          341                                                                                     ##STR268##                                                          342                                                                                     ##STR269##                                                          343                                                                                     ##STR270##                                                          344                                                                                     ##STR271##                                                          345                                                                                     ##STR272##                                                          346                                                                                     ##STR273##                                                          347                                                                                     ##STR274##                                                          348                                                                                     ##STR275##                                                          349                                                                                     ##STR276##                                                          350                                                                                     ##STR277##                                                          351                                                                                     ##STR278##                                                          352                                                                                     ##STR279##                                                          353                                                                                     ##STR280##                                                          354                                                                                     ##STR281##                                                          355                                                                                     ##STR282##                                                          356                                                                                     ##STR283##                                                          357                                                                                     ##STR284##                                                          358                                                                                     ##STR285##                                                          359                                                                                     ##STR286##                                                          360                                                                                     ##STR287##                                                          361                                                                                     ##STR288##                                                          362                                                                                     ##STR289##                                                          363                                                                                     ##STR290##                                                          364                                                                                     ##STR291##                                                          365                                                                                     ##STR292##                                                          366                                                                                     ##STR293##                                                          367                                                                                     ##STR294##                                                          368      MeO                                                                  369      EtO                                                                  370      n-PrO                                                                371      n-BuO                                                                372      MeSCH.sub.2                                                          373      EtSCH.sub.2                                                          374      n-PrSCH.sub.2                                                        375      n-BuSCH.sub.2                                                        376      i-PrSCH.sub.2                                                        377      n-C.sub.5 H.sub.4SCH.sub.2                                           378      MeS(CH.sub.2).sub.2                                                  379      EtS(CH.sub.2).sub.2                                                  380      n-PrS(CH.sub.2).sub.2                                                381      n-BuS(CH.sub.2).sub.2                                                382      MeOCH.sub.2                                                          383      EtOCH.sub.2                                                          384      n-PrOCH.sub.2                                                        385      n-BuOCH.sub.2                                                        386      N-PrOCH.sub.2                                                        387      n-C.sub.5 H.sub.4OCH.sub.2                                           388      MeO(CH.sub.2).sub.2                                                  389      EtO(CH.sub.2).sub.2                                                  390      n-PrO(CH.sub.2).sub.2                                                391      n-BuO(CH.sub.2).sub.2                                                392      PhSCH.sub.2                                                          393      PhOCH.sub.2                                                          394      PhCH.sub.2SCH.sub.2                                                  395      PHCH.sub.2 OCH.sub.2                                                 396                                                                                     ##STR295##                                                          397                                                                                     ##STR296##                                                          398                                                                                     ##STR297##                                                          399                                                                                     ##STR298##                                                          400                                                                                     ##STR299##                                                          401                                                                                     ##STR300##                                                          402                                                                                     ##STR301##                                                          403                                                                                     ##STR302##                                                          404                                                                                     ##STR303##                                                          405                                                                                     ##STR304##                                                          406                                                                                     ##STR305##                                                          407                                                                                     ##STR306##                                                          408                                                                                     ##STR307##                                                          409                                                                                     ##STR308##                                                          410      n-C.sub.17H.sub.39                                                   ______________________________________                                    

                  TABLE III                                                       ______________________________________                                        R.sup.1 = R.sup.2 = Me, R.sup.3 = H                                           Example No.                                                                            R.sup.4             m.p.                                             ______________________________________                                        411      H                                                                    412      Me                                                                   413      Et                                                                   414      n-Pr                                                                 415      i-Pr                                                                 416      c-Pr                                                                 417      n-Bu                                                                 418      i-Bu                                                                 419      s-Bu                                                                 420      t-Bu                                                                 421      n-C.sub.5 H.sub.4                                                    422                                                                                     ##STR309##                                                          423                                                                                     ##STR310##                                                          424                                                                                     ##STR311##                                                          425                                                                                     ##STR312##                                                          426                                                                                     ##STR313##                                                          427                                                                                     ##STR314##                                                          428                                                                                     ##STR315##                                                          429                                                                                     ##STR316##                                                          430                                                                                     ##STR317##                                                          431                                                                                     ##STR318##                                                          432                                                                                     ##STR319##                                                          433                                                                                     ##STR320##                                                          434                                                                                     ##STR321##                                                          435                                                                                     ##STR322##                                                          436                                                                                     ##STR323##                                                          437                                                                                     ##STR324##                                                          438                                                                                     ##STR325##                                                          439                                                                                     ##STR326##                                                          440                                                                                     ##STR327##                                                          441                                                                                     ##STR328##                                                          442                                                                                     ##STR329##                                                          443                                                                                     ##STR330##                                                          444                                                                                     ##STR331##                                                          445      NCCH.sub.2CH.sub.2                                                   446      CF.sub.3                                                             447      CF.sub.3CF.sub.2                                                     448      CF.sub.3CF.sub.2CF.sub.2                                             449      CF.sub.2CF.sub.2CH.sub.2                                             450      CF.sub.3CF.sub.2CF.sub.2CH.sub.2                                     451                                                                                     ##STR332##                                                          452                                                                                     ##STR333##                                                          453                                                                                     ##STR334##                                                          454                                                                                     ##STR335##                                                          455                                                                                     ##STR336##                                                          456                                                                                     ##STR337##                                                          457                                                                                     ##STR338##                                                          458                                                                                     ##STR339##                                                          459                                                                                     ##STR340##                                                          460                                                                                     ##STR341##                                                          461                                                                                     ##STR342##                                                          462                                                                                     ##STR343##                                                          463                                                                                     ##STR344##                                                          464                                                                                     ##STR345##                                                          465                                                                                     ##STR346##                                                          466                                                                                     ##STR347##                                                          467                                                                                     ##STR348##                                                          468                                                                                     ##STR349##                                                          469                                                                                     ##STR350##                                                          470                                                                                     ##STR351##                                                          471                                                                                     ##STR352##                                                          472                                                                                     ##STR353##                                                          473                                                                                     ##STR354##                                                          474                                                                                     ##STR355##                                                          475                                                                                     ##STR356##                                                          476                                                                                     ##STR357##                                                          477                                                                                     ##STR358##                                                          478                                                                                     ##STR359##                                                          479                                                                                     ##STR360##                                                          480                                                                                     ##STR361##                                                          481                                                                                     ##STR362##                                                          482                                                                                     ##STR363##                                                          483                                                                                     ##STR364##                                                          484                                                                                     ##STR365##                                                          485                                                                                     ##STR366##                                                          486                                                                                     ##STR367##                                                          487                                                                                     ##STR368##                                                          488      n-C.sub.7 H.sub.15                                                   489      n-C.sub.8 H.sub.17                                                   490      n-C.sub.9 H.sub.19                                                   491      n-C.sub.10H.sub.21                                                   492      n-C.sub.11 H.sub.23                                                  493      n-C.sub.12 H.sub.25                                                  494      n-C.sub.13 H.sub.27                                                  495                                                                                     ##STR369##                                                          496                                                                                     ##STR370##                                                          497                                                                                     ##STR371##                                                          498                                                                                     ##STR372##                                                          499                                                                                     ##STR373##                                                          500                                                                                     ##STR374##                                                          501                                                                                     ##STR375##                                                          502                                                                                     ##STR376##                                                          503                                                                                     ##STR377##                                                          504                                                                                     ##STR378##                                                          505                                                                                     ##STR379##                                                          506                                                                                     ##STR380##                                                          507                                                                                     ##STR381##                                                          508                                                                                     ##STR382##                                                          509                                                                                     ##STR383##                                                          510                                                                                     ##STR384##                                                          511                                                                                     ##STR385##                                                          512                                                                                     ##STR386##                                                          513                                                                                     ##STR387##                                                          514                                                                                     ##STR388##                                                          515                                                                                     ##STR389##                                                          516                                                                                     ##STR390##                                                          517                                                                                     ##STR391##                                                          518                                                                                     ##STR392##                                                          519                                                                                     ##STR393##                                                          520                                                                                     ##STR394##                                                          521                                                                                     ##STR395##                                                          522                                                                                     ##STR396##                                                          523                                                                                     ##STR397##                                                          524                                                                                     ##STR398##                                                          525                                                                                     ##STR399##                                                          526                                                                                     ##STR400##                                                          527                                                                                     ##STR401##                                                          528                                                                                     ##STR402##                                                          529                                                                                     ##STR403##                                                          530                                                                                     ##STR404##                                                          531                                                                                     ##STR405##                                                          532                                                                                     ##STR406##                                                          533                                                                                     ##STR407##                                                          534                                                                                     ##STR408##                                                          535                                                                                     ##STR409##                                                          536                                                                                     ##STR410##                                                          537                                                                                     ##STR411##                                                          538                                                                                     ##STR412##                                                          539                                                                                     ##STR413##                                                          540                                                                                     ##STR414##         162-163° C.                               541                                                                                     ##STR415##                                                          542                                                                                     ##STR416##                                                          543                                                                                     ##STR417##                                                          544                                                                                     ##STR418##                                                          545                                                                                     ##STR419##                                                          546                                                                                     ##STR420##                                                          547                                                                                     ##STR421##                                                          548                                                                                     ##STR422##                                                          549                                                                                     ##STR423##                                                          550                                                                                     ##STR424##                                                          551                                                                                     ##STR425##                                                          552                                                                                     ##STR426##                                                          553                                                                                     ##STR427##                                                          554                                                                                     ##STR428##                                                          555                                                                                     ##STR429##                                                          556                                                                                     ##STR430##                                                          557                                                                                     ##STR431##                                                          558                                                                                     ##STR432##                                                          559                                                                                     ##STR433##                                                          560                                                                                     ##STR434##                                                          561                                                                                     ##STR435##                                                          562                                                                                     ##STR436##                                                          563                                                                                     ##STR437##                                                          564                                                                                     ##STR438##                                                          565                                                                                     ##STR439##                                                          566                                                                                     ##STR440##                                                          567                                                                                     ##STR441##                                                          568                                                                                     ##STR442##                                                          569                                                                                     ##STR443##                                                          570                                                                                     ##STR444##                                                          571                                                                                     ##STR445##                                                          572                                                                                     ##STR446##                                                          573      MeO                                                                  574      EtO                                                                  575      n-PrO                                                                576      n-BuO                                                                577      MeSCH.sub.2                                                          578      EtSCH.sub.2                                                          579      n-PrSCH.sub.2                                                        580      n-BuSCH.sub.2                                                        581      i-PrSCH.sub.2                                                        582      n-C.sub.5 H.sub.4SCH.sub.2                                           583      MeS(CH.sub.2).sub.2                                                  584      EtS(CH.sub.2).sub.2                                                  585      n-PrS(CH.sub.2).sub.2                                                586      n-BuS(CH.sub.2).sub.2                                                587      MeOCH.sub.2                                                          588      EtOCH.sub.2                                                          589      n-PrOCH.sub.2                                                        590      n-BuOCH.sub.2                                                        591      n-PrOCH.sub.2                                                        592      n-C.sub.5 H.sub.4OCH.sub.2                                           593      MeO(CH.sub.2).sub.2                                                  594      EtO(CH.sub.2).sub.2                                                  595      n-PrO(CH.sub.2).sub.2                                                596      n-BuO(CH.sub.2).sub.2                                                597      PhSCH.sub.2                                                          598      PhOCH.sub.2                                                          599      PhCH.sub.2SCH.sub.2                                                  600      PHCH.sub.2OCH.sub.2                                                  601                                                                                     ##STR447##                                                          602                                                                                     ##STR448##                                                          603                                                                                     ##STR449##                                                          604                                                                                     ##STR450##                                                          605                                                                                     ##STR451##                                                          606                                                                                     ##STR452##                                                          607                                                                                     ##STR453##                                                          608                                                                                     ##STR454##                                                          609                                                                                     ##STR455##                                                          610                                                                                     ##STR456##                                                          611                                                                                     ##STR457##                                                          612                                                                                     ##STR458##                                                          613                                                                                     ##STR459##                                                          614                                                                                     ##STR460##                                                          615      n-C.sub.17H.sub.39                                                   ______________________________________                                    

                  TABLE IV                                                        ______________________________________                                        R.sup.1 = R.sup.2 = R.sup.3 = Me                                              Example No.                                                                            R.sup.4             m.p.                                             ______________________________________                                        616      H                                                                    617      Me                                                                   618      Et                                                                   619      n-Pr                                                                 620      i-Pr                                                                 621      c-Pr                                                                 622      n-Bu                                                                 623      i-Bu                                                                 624      s-Bu                                                                 625      t-Bu                                                                 626      n-C.sub.5 H.sub.4                                                    627                                                                                     ##STR461##                                                          628                                                                                     ##STR462##                                                          629                                                                                     ##STR463##                                                          630                                                                                     ##STR464##                                                          631                                                                                     ##STR465##                                                          632                                                                                     ##STR466##                                                          633                                                                                     ##STR467##                                                          634                                                                                     ##STR468##                                                          635                                                                                     ##STR469##                                                          636                                                                                     ##STR470##                                                          637                                                                                     ##STR471##                                                          638                                                                                     ##STR472##                                                          639                                                                                     ##STR473##                                                          640                                                                                     ##STR474##                                                          641                                                                                     ##STR475##                                                          642                                                                                     ##STR476##                                                          643                                                                                     ##STR477##                                                          644                                                                                     ##STR478##                                                          645                                                                                     ##STR479##                                                          646                                                                                     ##STR480##                                                          647                                                                                     ##STR481##                                                          648                                                                                     ##STR482##                                                          649                                                                                     ##STR483##                                                          650      NCCH.sub.2CH.sub.2                                                   651      CF.sub.3                                                             652      CF.sub.3CF.sub.2                                                     653      CF.sub.3CF.sub.2CF.sub.2                                             654      CF.sub.2CF.sub.2CH.sub.2                                             655      CF.sub.3CF.sub.2CF.sub.2CH.sub.2                                     656                                                                                     ##STR484##                                                          657                                                                                     ##STR485##                                                          658                                                                                     ##STR486##                                                          659                                                                                     ##STR487##                                                          660                                                                                     ##STR488##                                                          661                                                                                     ##STR489##                                                          662                                                                                     ##STR490##                                                          663                                                                                     ##STR491##                                                          664                                                                                     ##STR492##                                                          665                                                                                     ##STR493##                                                          666                                                                                     ##STR494##                                                          667                                                                                     ##STR495##                                                          668                                                                                     ##STR496##                                                          669                                                                                     ##STR497##                                                          670                                                                                     ##STR498##                                                          671                                                                                     ##STR499##                                                          672                                                                                     ##STR500##                                                          673                                                                                     ##STR501##                                                          674                                                                                     ##STR502##                                                          675                                                                                     ##STR503##                                                          676                                                                                     ##STR504##                                                          677                                                                                     ##STR505##                                                          678                                                                                     ##STR506##                                                          679                                                                                     ##STR507##                                                          680                                                                                     ##STR508##                                                          681                                                                                     ##STR509##                                                          682                                                                                     ##STR510##                                                          683                                                                                     ##STR511##                                                          684                                                                                     ##STR512##                                                          685                                                                                     ##STR513##                                                          686                                                                                     ##STR514##                                                          687                                                                                     ##STR515##                                                          688                                                                                     ##STR516##                                                          689                                                                                     ##STR517##                                                          690                                                                                     ##STR518##                                                          691                                                                                     ##STR519##                                                          692                                                                                     ##STR520##                                                          693      n-C.sub.7 H.sub.15                                                   694      n-C.sub.8 H.sub.17                                                   695      n-C.sub.9 H.sub.19                                                   696      n-C.sub.10H.sub.21                                                   697      n-C.sub.11 H.sub.23                                                  698      n-C.sub.12 H.sub.25                                                  699      n-C.sub.13 H.sub.27                                                  700                                                                                     ##STR521##                                                          701                                                                                     ##STR522##                                                          702                                                                                     ##STR523##                                                          703                                                                                     ##STR524##                                                          704                                                                                     ##STR525##                                                          705                                                                                     ##STR526##                                                          706                                                                                     ##STR527##                                                          707                                                                                     ##STR528##                                                          708                                                                                     ##STR529##                                                          709                                                                                     ##STR530##                                                          710                                                                                     ##STR531##                                                          711                                                                                     ##STR532##                                                          712                                                                                     ##STR533##                                                          713                                                                                     ##STR534##                                                          714                                                                                     ##STR535##                                                          715                                                                                     ##STR536##                                                          716                                                                                     ##STR537##                                                          717                                                                                     ##STR538##                                                          718                                                                                     ##STR539##                                                          719                                                                                     ##STR540##                                                          720                                                                                     ##STR541##                                                          721                                                                                     ##STR542##                                                          722                                                                                     ##STR543##                                                          723                                                                                     ##STR544##                                                          724                                                                                     ##STR545##                                                          725                                                                                     ##STR546##                                                          726                                                                                     ##STR547##                                                          727                                                                                     ##STR548##                                                          728                                                                                     ##STR549##                                                          729                                                                                     ##STR550##                                                          730                                                                                     ##STR551##                                                          731                                                                                     ##STR552##                                                          732                                                                                     ##STR553##                                                          733                                                                                     ##STR554##                                                          734                                                                                     ##STR555##                                                          735                                                                                     ##STR556##                                                          736                                                                                     ##STR557##                                                          737                                                                                     ##STR558##                                                          738                                                                                     ##STR559##                                                          739                                                                                     ##STR560##                                                          740                                                                                     ##STR561##                                                          741                                                                                     ##STR562##                                                          742                                                                                     ##STR563##                                                          743                                                                                     ##STR564##                                                          744                                                                                     ##STR565##                                                          745                                                                                     ##STR566##                                                          746                                                                                     ##STR567##                                                          747                                                                                     ##STR568##                                                          748                                                                                     ##STR569##                                                          749                                                                                     ##STR570##                                                          750                                                                                     ##STR571##                                                          751                                                                                     ##STR572##                                                          752                                                                                     ##STR573##                                                          753                                                                                     ##STR574##                                                          754                                                                                     ##STR575##                                                          755                                                                                     ##STR576##                                                          756                                                                                     ##STR577##                                                          757                                                                                     ##STR578##                                                          758                                                                                     ##STR579##                                                          759                                                                                     ##STR580##                                                          760                                                                                     ##STR581##                                                          761                                                                                     ##STR582##                                                          762                                                                                     ##STR583##                                                          763                                                                                     ##STR584##                                                          764                                                                                     ##STR585##                                                          765                                                                                     ##STR586##                                                          766                                                                                     ##STR587##                                                          767                                                                                     ##STR588##                                                          768                                                                                     ##STR589##                                                          769                                                                                     ##STR590##                                                          770                                                                                     ##STR591##                                                          771                                                                                     ##STR592##                                                          772                                                                                     ##STR593##                                                          773                                                                                     ##STR594##                                                          774                                                                                     ##STR595##                                                          775                                                                                     ##STR596##                                                          776                                                                                     ##STR597##                                                          777                                                                                     ##STR598##                                                          778      MeO                                                                  779      EtO                                                                  780      n-PrO                                                                781      n-BuO                                                                782      MeSCH.sub.2                                                          783      EtSCH.sub.2                                                          784      n-PrSCH.sub.2                                                        785      n-BuSCH.sub.2                                                        786      i-PrSCH.sub.2                                                        787      n-C.sub.5 H.sub.4SCH.sub.2                                           788      MeS(CH.sub.2).sub.2                                                  789      EtS(CH.sub.2).sub.2                                                  790      n-PrS(CH.sub.2).sub.2                                                791      n-BuS(CH.sub.2).sub.2                                                792      MeOCH.sub.2                                                          793      EtOCH.sub.2                                                          794      n-PrOCH.sub.2                                                        795      n-BuOCH.sub.2                                                        796      N-PrOCH.sub.2                                                        797      n-C.sub.5 H.sub.4OCH.sub.2                                           798      MeO(CH.sub.2).sub.2                                                  799      EtO(CH.sub.2).sub.2                                                  800      n-PrO(CH.sub.2).sub.2                                                801      n-BuO(CH.sub.2).sub.2                                                802      PhSCH.sub.2                                                          803      PhOCH.sub.2                                                          804      PhCH.sub.2SCH.sub.2                                                  805      PHCH.sub.2 OCH.sub.2                                                 806      191                                                                                                ##STR599##                                      807      192                                                                                                ##STR600##                                      808                                                                                     ##STR601##                                                          809                                                                                     ##STR602##                                                          810                                                                                     ##STR603##                                                          811                                                                                     ##STR604##                                                          812                                                                                     ##STR605##                                                          813                                                                                     ##STR606##                                                          814                                                                                     ##STR607##                                                          815                                                                                     ##STR608##                                                          816                                                                                     ##STR609##                                                          817                                                                                     ##STR610##                                                          818                                                                                     ##STR611##                                                          819                                                                                     ##STR612##                                                          820      n-C.sub.17H.sub.39                                                   ______________________________________                                    

B. Testing the mould-resistance of coatings

The substance to be tested for its fungicidal activity is incorporatedby means of a dissolver into the (emulsion) paint at the desiredconcentration. The paint is then brushed onto a suitable support on bothsides.

In order to obtain results approximating those in practice, some of thetest pieces are leached with flowing water (24 h; 20° C.) prior to thetest for mould resistance.

The so prepared test pieces are placed on an agar nutrient medium. Testpieces and nutrient medium are infected with varieties of fungi. Afterstorage for 1 to 3 weeks at 29°±1° C. and 80 to 90% relative humidity,the samples are inspected. The coating is permanently mould-resistant ifthe test piece remains free of fungus or if at most a slight marginalattack can be observed.

For the infection, fungal spores of the following nine moulds are usedwhich are known as destroyers of coatings or are frequently encounteredon coatings:

1. Alternaria tenuis

2. Aspergillus flavus

3. Aspergillus niger

4. Aspergillus ustus

5. Cladosporium herbarum

6. Paecilomyces variotii

7. Penicillium citrinum

8. Aureobasidium pullulans

9. Stachybotrys atra Corda

The following table V shows the active compound concentrations at whichthe coating test piece remains free of fungus (concentrations based onsolids content of the emulsion paint). ##STR613##

                  TABLE V                                                         ______________________________________                                                    without load                                                                          after watering                                                                           discoloration                                  ______________________________________                                        Known Example A                                                                             0.3%       >3%       none                                       Known Example B                                                                             0.2%      0.3%       from 0.3%                                  according to the invention                                                                  0.6%      2.0%       none                                       Example 7                                                                     ______________________________________                                    

We claim:
 1. Thiazolylpyrazolinone derivatives of the formula ##STR614##in which R¹, R², R³ independently of each other each represent hydrogen,alkyl or halogen, andR⁴ represents hydrogen or unsubstituted orsubstituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, alkyl(cycloalkyl), alkenyl (cycloalkenyl), alkoxy, alkylthio, aralkoxy,aralkylthio, aralkyl, aryl, hetaryl, aryloxy, hetaryloxy, arylthio,hetarylthio, alkoxycarbonyl, alkoxycarbonalalkyl or cyanoalkyl, or theiracid addition products or metal complexes, wherein if R⁴ representssubstituted hetaryl, then the substituents are selected from the groupconsisting of halogen, alkyl, alkoxy or alkylthio.
 2. Compounds of theformula (I) according to claim 1, in which ##STR615## R¹, R², R³ denotehydrogen or methyl, R⁴ denotes unsubstituted or substituted alkyl,cycloalkyl, alkenyl, aralkyl or aryl.
 3. Compounds of the formula (I)according to claim 1, in whichR¹ denotes hydrogen, R², R³ denotehydrogen or methyl, R⁴ denotes unsubstituted or substituted alkyl,cycloalkyl, aralkyl or aryl.
 4. Compounds of the formula (I) accordingto claim 1, in whichR¹, R² and R³ denote hydrogen, R⁴ denotesunsubstituted or substituted alkyl or cycloalkyl.
 5. Process for thepreparation of novel thiazolylpyrazolinone derivatives of the formula(I) according to claim 1, characterized in that thiocarbamoyl compoundsof the formula (II) ##STR616## in which R³ and R⁴ have the meaningsgiven above are reacted, in the presence or absence of a solvent ordiluent and in the presence or absence of a base, with compounds of theformula (III) ##STR617## in which R¹ and R² have the meanings givenabove and X represents a leaving group.
 6. A composition for protectinga technical material from attack and destruction by a microorganismcomprising a protective effective amount of a compound of the formula(I) according to claim 1 and an extender.
 7. A method of protecting atechnical material from attack and destruction by a microorganismcomprising applying to the technical material or admixing with thetechnical material a protective effective amount of a compound of theformula (I) according to claim 1.